JP2019006851A - Antireflection coating composition and antireflection film - Google Patents

Abstract

An antireflective coating composition capable of imparting excellent scratch resistance to the surface of a cured coating film, and an antireflection film having the cured coating film.
A low refractive index agent, an active energy ray-curable compound, a poly (perfluoroalkylene ether) chain having a (meth) acryloyl group, and an α-aminoacetophenone compound capable of generating radical species by photolysis. An antireflective coating composition containing a fluorine-containing acetophenone derivative represented by formulas (1) and (2) and a cured coating film thereof.

[Selection] Figure 1

Description

  The present invention relates to an antireflection coating composition capable of obtaining a coating film having excellent scratch resistance and an antireflection film using the antireflection coating composition.

  Anti-glare and anti-reflection coatings such as AG, AG / LR, and Clear / LR are applied to the surface layer of the polarizing plate that is the top surface of the liquid crystal display. Antifouling properties such as fingerprint resistance are required. Here, the fingerprint resistance means that the fingerprint is difficult to adhere to the article, or that the fingerprint can be easily wiped off even if the fingerprint is attached to the article. Among the coatings having antiglare properties and antireflection properties, clear / LR is excellent from the viewpoint of transparency of the coating film.

  Currently, many polarizing plates in mass production for liquid crystal display devices, in particular, are made by stretching and adsorbing dichroic materials such as iodine and dichroic dyes onto a base film made of polyvinyl alcohol film. A film in which an optically transparent protective film having mechanical strength is bonded to both surfaces or one surface of an oriented polarizing film is used. And as a protective film, a triacetyl cellulose (TAC) film is usually used. And as for the coating film which has the said anti-glare property and anti-reflective property, for example, a clear / LR layer is dozens to several on the coating-film layer (base layer) about 10 micrometers thick formed on the TAC film. It is formed as a coating film having a thickness of about 100 nm.

  A coating film having antiglare property and antireflection property is required to have hard coat performance, that is, scratch resistance on the surface, in addition to antireflection performance and antifouling performance. In particular, the antireflection layer has a film thickness of only about several tens to several hundreds of nanometers, and a stronger scratch resistance is required. As a method for improving the scratch resistance of the antireflection layer, a method using a hard coat material containing a polyfunctional monomer such as polyfunctional (meth) acrylate is known. However, when this hard coat material is used, an antireflection layer having a surface hardness of the cured coating film improved to some extent can be obtained, but the scratch resistance is insufficient.

  In response to this problem, a fluorine-containing polymerizable resin having a perfluoroalkylene ether chain, a silicone group and a polymerizable unsaturated group is added to the coating composition for the antireflection film to impart slipperiness to the surface of the antireflection layer. It has been proposed to improve the scratch resistance (see, for example, Patent Document 1).

JP 2013-181039 A

  The antireflection coating composition to which the fluorine-containing polymerizable resin provided in Patent Document 1 is added has a certain effect on the scratch resistance, but is compatible with a non-fluorine-based active energy ray-curable compound. As a molecular design, it has a polar group near the poly (perfluoroalkylene ether) chain, which affects the shape of the poly (perfluoroalkylene ether) chain on the surface of the coating film. The non-fluorine moiety in the compound is difficult because the performance inherent in the alkylene ether chain cannot be sufficiently exerted, and further, due to the structural problem of disposing a polymerizable unsaturated group via another monomer-derived structure. The ratio is high, and there is a limit to increasing the density of fluorine atoms on the outermost surface of the cured coating film. For this reason, from the viewpoint of further scratch resistance It is less likely able to answer to the high demands of recent years.

  In view of the above circumstances, the problem to be solved by the present invention is to provide an antireflection coating composition capable of imparting excellent scratch resistance to the surface of a cured coating film, and an antireflection film having the cured coating film. That is.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have applied a Michael addition reaction to a poly (perfluoroalkylene ether) chain having a (meth) acryloyl group to obtain an α-aminoacetophenone series. By using a fluorine-containing acetophenone derivative obtained by introducing a structural unit capable of generating radical species by photolysis, fluorine atoms can be arranged at high density on the outermost surface of the cured product, and scratch resistance is improved. It can be remarkably improved, and since the compound before splitting contains a sufficient amount of non-fluorine moieties, it has excellent compatibility with non-fluorinated polymerizable compounds and excellent transparency of the resulting cured coating film. The present invention has been completed.

  That is, the present invention is capable of generating radical species by low refractive index agent (I), active energy ray-curable compound (II), poly (perfluoroalkylene ether) chain having (meth) acryloyl group, and photolysis. A fluorinated acetophenone derivative (III), which is a Michael adduct with an α-aminoacetophenone compound, and an antireflection film obtained by curing the antireflective coating composition. It is.

  The composition of the present invention to which a fluorine-containing acetophenone derivative is added has an effect of minimizing the surface free energy peculiar to fluorine atoms when applied to a substrate, and the derivative segregates on the surface. It is possible to impart remarkable scratch resistance to the outermost surface of the cured product. Further, since the derivative has a sufficient structural unit for compatibility with a non-fluorine compound, the transparency of the cured coating film is not impaired. Furthermore, since the fluorine-containing acetophenone derivative used in the present invention can be combined with other curable components in the composition by splitting with active energy rays and generating radicals, the outermost surface of the cured coating film The perfluoroalkylene ether chain in the fluorinated acetophenone derivative is more firmly fixed to the surface, and it is possible to suppress deterioration such as scratch resistance due to long-term storage, and further, a polar group in the vicinity of the perfluoroalkylene ether chain. Therefore, it is possible to suppress changes in the structure of the polymer chain that would impair the performance inherent to this perfluoroalkylene ether chain, and it is extremely useful as an antireflection film or the like provided on the outermost surface of a liquid crystal display. .

^{1 is} a ¹ H-NMR chart of a compound (M1) obtained in Synthesis Example 14. ^{1 is} a ¹ H-NMR chart of a compound (M2) obtained in Synthesis Example 15. ^{1 is} a ¹ H-NMR chart of a compound (M9) obtained in Synthesis Example 16. ^{1 is} a ¹ H-NMR chart of a compound (M18) obtained in Synthesis Example 19. 2 is a ¹ H-NMR chart of a compound (M20) obtained in Synthesis Example 20.

  The low refractive index agent (I) used in the present invention preferably has a refractive index of 1.44 or less, more preferably 1.40 or less. The low refractive index agent may be either inorganic or organic.

  Examples of the inorganic low refractive index agent (I) include fine particles having voids and fine metal fluoride particles. Examples of the fine particles having voids include those in which fine particles are filled with gas, and those having a porous structure containing gas inside. Specific examples include hollow silica fine particles and silica fine particles having a nanoporous structure. Examples of the metal fluoride fine particles include magnesium fluoride, aluminum fluoride, calcium fluoride, and lithium fluoride.

  Among these inorganic low refractive index agents (I), hollow silica fine particles are preferable. Further, these inorganic low refractive index agents (I) can be used alone or in combination of two or more. As these inorganic low refractive index agents (I), any of crystalline, sol, and gel can be used.

  The shape of the silica fine particles may be spherical, chain-like, needle-like, plate-like, scale-like, rod-like, fiber-like, or indefinite shape, and among these, spherical or needle-like is preferable. Moreover, when the shape is spherical, the average particle diameter of the silica fine particles is preferably 5 to 100 nm, more preferably 20 to 80 nm, and further preferably 40 to 70 nm. When the average particle diameter of the spherical fine particles is within this range, excellent transparency can be imparted to the low refractive index layer.

  On the other hand, examples of the organic low refractive index agent (I) include fine particles having voids and fluorine-containing copolymers. The fine particles having voids are preferably hollow polymer fine particles. The hollow polymer fine particles are prepared by, in an aqueous dispersion stabilizer solution, (1) at least one crosslinkable monomer, (2) a polymerization initiator, (3) a polymer obtained from at least one crosslinkable monomer, or at least one. A mixture of a copolymer of a kind of crosslinkable monomer and at least one kind of monofunctional monomer, and a poorly water-soluble solvent having low compatibility with the above (1) to (3) is dispersed and suspended. It can manufacture by performing superposition | polymerization. Here, the crosslinkable monomer is one having two or more polymerizable groups, and the monofunctional monomer is one having one polymerizable group.

  The fluorine-containing copolymer used as the organic low refractive index agent (I) is a resin having a low refractive index because the resin contains many fluorine atoms. Examples of the fluorine-containing copolymer include a copolymer using vinylidene fluoride and hexafluoropropylene as monomer raw materials.

  The ratio of each monomer that is a raw material of the fluorinated copolymer is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, further preferably 40 to 70% by mass, and hexafluorofluorovinylidene fluoride. The proportion of propylene is preferably 5 to 50% by mass, more preferably 10 to 50% by mass, and still more preferably 15 to 45%. As this other monomer, tetrafluoroethylene may be used in the range of 0 to 40% by mass.

  The fluorine-containing copolymer includes, as monomer components of other raw materials, fluoroethylene, trifluoroethylene, chlorotrifluoroethylene, 1,2-dichloro-1,2-difluoroethylene, 2-bromo-3,3, 3-trifluoroethylene, 3-bromo-3,3-difluoropropylene, 3,3,3-trifluoropropylene, 1,1,2-trichloro-3,3,3-trifluoropropylene, α-trifluoromethacrylic A polymerizable monomer having a fluorine atom such as an acid can be used. These other raw material monomer components are preferably used in the raw material monomer of the fluorine-containing copolymer in an amount of 20% by mass or less.

  The fluorine content in the fluorine-containing copolymer is preferably 60 to 70% by mass, more preferably 62 to 70% by mass, and further preferably 64 to 68% by mass. When the fluorine content of the fluorine-containing copolymer is within this range, the solubility in a solvent is good, and excellent adhesion to various substrates is exhibited. High transparency, low refractive index, excellent machine A thin film having sufficient strength can be formed.

  The molecular weight of the fluorine-containing copolymer is preferably 5,000 to 200,000, more preferably 10,000 to 100,000, in terms of polystyrene-equivalent number average molecular weight. When the molecular weight of the fluorinated copolymer is within this range, the viscosity of the resulting resin is in a range having excellent coating properties. The refractive index of the fluorinated copolymer itself is preferably 1.45 or less, more preferably 1.42 or less, and even more preferably 1.40 or less.

  The active energy ray-curable compound (II) used in the present invention is not particularly limited as long as it is a compound having a photopolymerizable functional group that can be polymerized or crosslinked by irradiation with active energy rays such as ultraviolet rays. it can.

  Examples of the active energy ray-curable compound (II) include an active energy ray-curable monomer (II-1). Examples of the monomer (II-1) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and polyethylene having a number average molecular weight in the range of 150 to 1,000. Glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) having a number average molecular weight in the range of 150 to 1000 Acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate Hydroxypivalate ester neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dicyclopentenyl (meth) acrylate, methyl (meth) acrylate, propyl ( (Meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, Aliphatic alkyl (meth) acrylates such as sodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, glycerol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3 -Chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, 2- (dimethylamino) Ethyl (meth) acrylate, γ- (meth) acryloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxydipropylene glyco (Meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydipropylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, polybutadiene ( (Meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polystyrylethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl ( (Meth) acrylate, dicyclopentenyl (meth) acrylate, isoborni (Meth) acrylate, methoxylated tricyclodecanyloxy triene (meth) acrylate, phenyl (meth) acrylate.

  Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra ( A trifunctional or higher polyfunctional (meth) acrylate such as (meth) acrylate is preferred. These active energy ray-curable monomers (II-1) can be used alone or in combination of two or more.

  In the present invention, “(meth) acrylate” refers to one or both of methacrylate and acrylate, and “(meth) acryloyl group” refers to one or both of methacryloyl group and acryloyl group. “Acrylic acid” refers to one or both of methacrylic acid and acrylic acid.

  Moreover, active energy ray-curable resin (II-2) can also be used as the active energy ray-curable compound (II). Examples of the active energy ray-curable resin (II-2) include urethane (meth) acrylate resins, unsaturated polyester resins, epoxy (meth) acrylate resins, polyester (meth) acrylate resins, and acrylic (meth) acrylate resins. However, in the present invention, a urethane (meth) acrylate resin is particularly preferable from the viewpoint of transparency and low shrinkage.

  The urethane (meth) acrylate resin used here is a resin having a urethane bond and a (meth) acryloyl group obtained by reacting an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound with a (meth) acrylate compound having a hydroxyl group. Is mentioned.

  Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl- 1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate , Hydrogenated tolylene diisocyanate, hydrogenated xylile Examples include diisocyanate, hydrogenated tetramethylxylylene diisocyanate, cyclohexyl diisocyanate, and the aromatic polyisocyanate compound includes tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, Examples include toridine diisocyanate and p-phenylene diisocyanate.

  On the other hand, examples of the acrylate compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1, Monovalent dihydric alcohols such as 5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, and hydroxypivalate neopentyl glycol mono (meth) acrylate ( Meth) acrylate; trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate Mono- or di (meth) acrylates of trivalent alcohols such as relate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or hydroxyl groups obtained by modifying some of these alcoholic hydroxyl groups with ε-caprolactone Mono- and di (meth) acrylates having a monofunctional hydroxyl group and tri- or more functional (meth) acryloyl such as pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. A compound having a group, or a polyfunctional (meth) acrylate having a hydroxyl group obtained by modifying the compound with ε-caprolactone; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, poly (Meth) acrylate compounds having an oxyalkylene chain such as propylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate; polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-polyoxypropylene mono (meth) (Meth) acrylate compounds having a block structure oxyalkylene chain such as acrylate; random structures such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate And (meth) acrylate compounds having an oxyalkylene chain.

  The reaction between the aliphatic polyisocyanate compound or the aromatic polyisocyanate compound and the acrylate compound having a hydroxyl group can be performed by a conventional method in the presence of a urethanization catalyst. Specific examples of urethanization catalysts that can be used here include amines such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine, phosphines such as triphenylphosphine and triethylphosphine, dibutyltin dilaurate, octyltin trilaurate, and octyl. Examples thereof include organotin compounds such as tin diacetate, dibutyltin diacetate, and tin octylate, and organometallic compounds such as zinc octylate.

  Among these urethane acrylate resins, those obtained by reacting an aliphatic polyisocyanate compound with a (meth) acrylate compound having a hydroxyl group are excellent in transparency of the cured coating film and have good sensitivity to active energy rays. It is preferable from the viewpoint of excellent curability.

  Next, the unsaturated polyester resin is a curable resin obtained by polycondensation of α, β-unsaturated dibasic acid or acid anhydride thereof, aromatic saturated dibasic acid or acid anhydride thereof, and glycols. The α, β-unsaturated dibasic acid or its acid anhydride includes maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof. As aromatic saturated dibasic acid or acid anhydride thereof, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride and these Examples include esters. Examples of the aliphatic or alicyclic saturated dibasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof. As glycols, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, Examples include tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl) propane, and others. In addition, oxides such as ethylene oxide and propylene oxide can be used in the same manner.

  Next, as an epoxy vinyl ester resin, (meth) acrylic acid is reacted with an epoxy group of an epoxy resin such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, or a cresol novolak type epoxy resin. What is obtained is mentioned. These active energy ray-curable resins (II-2) can be used alone or in combination of two or more.

  The active energy ray-curable monomer (II-1) and the active energy ray-curable resin (II-2) may be used alone or in combination.

  The mass ratio between the low refractive index agent (I) and the active energy ray-curable compound (II) is preferably in the range of (I) :( II) = 30: 70 to 90:10, 40:60 to 80: The range of 20 is more preferable, and the range of 50:50 to 70:30 is more preferable.

  The fluorine-containing acetophenone derivative (III) used in the present invention is a Michael adduct of a poly (perfluoroalkylene ether) chain having a (meth) acryloyl group and an α-aminoacetophenone compound capable of generating radical species by photolysis. It is.

  Examples of the fluorine-containing acetophenone derivative (III) include compounds having a structure represented by the following general formula (1) or (2).

[In the formulas (1) and (2), A is a direct bond, a divalent or trivalent linking group, m is 1 for a direct bond or a divalent linking group, and a trivalent linking group. m is 2. Y is the following general formula (3) or the following general formula (4)

(X ¹ and X ² are each independently a C 2-6 linear or branched alkylene group or oxyalkylene group which may have a substituent, and X ¹ and X ² are The constituting carbon atoms may be bonded to each other directly or via a linear or branched alkylene group having 2 to 6 carbon atoms which may have a substituent, and X ³ has a substituent. A linear or branched alkylene group or oxyalkylene group having 2 to 6 carbon atoms, and R ⁵ and R ⁶ are each independently an aliphatic group which may have a substituent. An aryl group which may have a group or a substituent),
R is independently a hydrogen atom, a halogen atom or an aliphatic group which may have a substituent, n is each independently an integer of 0 to 4, and R ¹ and R ² are each independently An aliphatic group which may have a substituent or an aryl group which may have a substituent, and R ¹ and R ² may be combined together to form a ring, and R ³ is An aliphatic group which may have a substituent or an aryl group which may have a substituent, R ⁴ is a hydrogen atom, a halogen atom or a monovalent organic group, and PFPE is a poly (perfluoroalkylene) Ether) chain. ]

  The compounds represented by the general formulas (1) and (2) are divided by a poly (perfluoroalkylene ether) chain (hereinafter sometimes referred to as a PFPE chain) as a constituent element and active energy rays or the like to generate radicals. And a portion that can be generated. By having such a molecular structure, for example, when compounded in an active energy ray-curable composition, the compound moves to the gas-liquid interface and exists on the outermost surface by the surface segregation function of fluorine atoms during the curing reaction. However, by generating radicals, the compound after splitting (PFPE chain-containing compound) can strongly bond with other curable components, and can give remarkable scratch resistance to the surface of the cured coating film. It becomes. From the viewpoint of more preferably these effects, the compound of the general formula (1) is preferable.

  In addition, since the compounds represented by the general formulas (1) and (2) contain a large amount of non-fluorine moieties, they can be dissolved in a non-fluorine active energy ray-curable compound or an organic solvent (phase). Since the solubility is good, the storage stability as a composition or solution and the transparency of the resulting cured coating film are also good. Furthermore, since it is compatible with other fluorinated surfactants, it can be mixed with other fluorinated surfactants and stored as a fluorinated additive.

  The fluorine-containing acetophenone derivatives represented by the general formulas (1) and (2) can be synthesized by applying a Michael addition reaction to the acryloyl group of the PFPE chain-containing compound having an acryloyl group. For this reason, constituent elements other than the PFPE chain-containing compound having an acryloyl group which is a Michael acceptor have a function as a Michael donor and have an acetophenone-like structure that can be split by active energy rays or the like. Anything is acceptable.

Y in the general formulas (1) and (2) is represented by the general formula (3) or the general formula (4). In the general formula (3), X ¹ and X ² are each independently a linear or branched alkylene group or oxyalkylene group having 2 to 6 carbon atoms which may have a substituent. And the carbon atoms constituting X ¹ and X ² may be bonded to each other directly or via a linear or branched alkylene group having 2 to 6 carbon atoms which may have a substituent. .

Here, examples of the substituent include a substituent composed of a monovalent nonmetallic atom excluding a hydrogen atom. Specifically, for example, halogen atom (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, Amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N- Alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group , Acylthio group, acylamino group, N-alkyl acyl Mino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group, N′- Alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl -N-alkylureido group, N ', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N', N'-diaryl -N-alkylureido group, N ', N'-diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N- Arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (-S O ₃ H) and its conjugate base group (referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-aryl Sulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N- Arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂ ) and its conjugate base group (referred to as phosphonato group), dialkyl Phosphono group (—PO ₃ (alkyl) ₂ ) “alkyl = alkyl group, hereinafter the same”, dia Lille phosphono group (—PO ₃ (aryl) ₂ ) “aryl = aryl group, hereinafter the same”, alkylarylphosphono group (—PO ₃ (alkyl) (aryl)), monoalkylphosphono group (—PO ₃ (alkyl)) ) And conjugated base groups (referred to as alkylphosphonate groups), monoarylphosphono groups (—PO ₃ H (aryl)) and conjugated base groups (referred to as arylphosphonate groups), phosphonooxy groups (—OPO ₃ H) ₂ ) and its conjugate base group (referred to as phosphonatoxy group), dialkylphosphonooxy group (—OPO ₃ H (alkyl) ₂ ), diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy Group (—OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group (referred to as alkylphosphonatooxy group), monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonatoxy group), Examples include cyano group, nitro group, aryl group, alkenyl group, alkynyl group, heterocyclic group, silyl group and the like.

  Specific examples of the alkyl group in these substituents include linear, branched, and cyclic alkyl groups having 1 to 18 carbon atoms, such as a methyl group, an ethyl group, and a propyl group. Group, n-butyl group, t-butyl group; s-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group , Hexadecyl group, heptadecyl group, octadecyl group, isopropyl group, second butyl group, isobutyl group, third butyl group, 2-ethylbutyl group, isopentyl group, 1-methylpentyl group, 1,3-dimethylbutyl group, 1- Methylhexyl group, isoheptyl group, 1,1,3,3-tetramethylbutyl group, 2,2,4,4-tetramethylbutyl group, 1 Methylheptyl group, 3-methylheptyl group, 2-ethylhexyl group, 1,1,3-trimethylhexyl group, 1,1,3,3-tetramethylpentyl group, isodecyl group, 1-methylundecyl group or 1, 1,3,3,5,5-hexamethylhexyl group, dodecyl group, tetradecyl group, octadecyl group, and other linear or branched alkyl groups, cycloheptyl group, cyclohexyl group, cyclopentyl group, and other cycloalkyl groups Is mentioned.

  Specific examples of the aryl group in the substituent include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxy Phenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxy Carbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophenyl group, sulfophenyl group, sulphonatophenyl group, phosphonopheny Groups, phosphonium Hona preparative phenyl group.

  Examples of the alkenyl group include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like, and examples of alkynyl group include ethynyl group, 1-propynyl group. Group, 1-butynyl group, trimethylsilylethynyl group and the like.

  In addition, the linear or branched alkylene group or oxyalkylene group having 2 to 6 carbon atoms specifically includes a chain or branched methylene group, propylene group, butylene group, oxymethylene group, oxypropylene. Group, oxybutylene group and the like.

  Specifically, the general formula (3) has the following structure.

R ⁵ and R ⁶ in the general formula (4) are each independently an aliphatic group which may have a substituent or an aryl group which may have a substituent. Examples of the aliphatic group that may have a substituent include an alkyl group, an alkenyl group, and an alkynyl group, each of which may have a substituent, and examples of the substituent include the above-described substituents. As the alkyl group, alkenyl group and alkynyl group, the same groups as described above can be exemplified.

  In addition, an aryl group as an aryl group which may have a substituent is one in which 1 to 3 benzene rings form a condensed ring, or a benzene ring and a 5-membered unsaturated ring form a condensed ring Is mentioned. Specifically, for example, phenyl group, methoxyphenyl group, ethoxyphenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, α-methylbenzyl group, αα-dimethyl Examples include benzyl group, phenethyl group naphthyl group, anthryl group, phenanthryl group, indenyl group, acenaphthenyl group, and fluorenyl group. In these, a phenyl group and a naphthyl group are more preferable.

  Examples of the substituent as the aryl group having the substituent include those having a group composed of a monovalent nonmetallic atom excluding a hydrogen atom as a substituent on the ring-forming carbon atom of the aryl group. Things.

  Preferable specific examples of the aryl group having a substituent include a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group, a chloromethylphenyl group, and a trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, Boxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonopheny Group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group and the like.

In the general formulas (1) and (2), R ¹ and R ² are each independently an aliphatic group which may have a substituent or an aryl group which may have a substituent, and R ¹ and R ² may be combined together to form a ring. Examples of the “optionally substituted aliphatic group or the optionally substituted aryl group” in R ¹ and R ² can include those described above, and the number of carbon atoms is 1 to 12. And a linear alkyl group having 1 to 6 carbon atoms is more preferable.

R ³ in the general formulas (1) and (2) is an aliphatic group which may have a substituent or an aryl group which may have a substituent, and this is also the same as described above. A linear alkyl group having 1 to 12 carbon atoms is preferable, and a linear alkyl group having 1 to 6 carbon atoms is more preferable.

R ⁴ in the general formulas (1) and (2) is a hydrogen atom, a halogen atom or a monovalent organic group, and examples of the monovalent organic group include an alkyl group having 1 to 6 carbon atoms, carbon alkyloxy group having the number of atoms of 1 to 6, an aryl group, an aryloxy group, or ^-X 4 ^-X 5 -X organic group represented by ⁶ [However, ^{X 4} also have a single bond or a substituent A good alkylene group having 1 to 6 carbon atoms, X ⁵ is a carbonyl group, a thiocarbonyl group, —OCONH—, —NHCOO—, or —NHCONH—, and X ⁶ is —NR ⁷ R ⁸ (where R ⁷ and R ⁸ are each independently an aliphatic group which may have a substituent or an aryl group which may have a substituent.), Or the following general formula (5)

(However, X ^7, X ⁸ are each independently a linear or branched alkylene group or an oxyalkylene group having optionally 2 to 6 carbon atoms which may have a substituent, X ⁷ and X ⁸ may be bonded to each other directly or via a linear or branched alkylene group having 2 to 6 carbon atoms which may have a substituent, and X ⁹ is a single atom. A bond, an oxygen atom, or —NR ⁹ — (wherein R ⁹ is a hydrogen atom or a linear or branched alkyl group having 2 to 6 carbon atoms which may have a substituent). )] Is preferable.

As the substituent of the alkylene chain having 1 to 6 carbon atoms which may have the substituent of X ⁴ , any of the above-mentioned ones can be exemplified, and has a substituent of R ⁷ and R ^8. An aliphatic group which may be substituted or an aryl group which may have a substituent is the same as described above. In the general formula (5), X ⁷ and X ⁸ are the same as the general formulas X ¹ and X ² . Any of the above-mentioned substituents for R ⁹ can also be mentioned.

  Furthermore, R in the general formulas (1) and (2) represents a hydrogen atom or a substituent on a carbon atom forming a benzene ring, and this substituent is the same as described above. The benzene ring has four substituents, which may be the same or different.

As the fluorine-containing acetophenone derivative of the present invention represented by the general formulas (1) and (2), in particular, Y in the general formulas (1) and (2) is represented by the following formula (6).
R is hydrogen, R ¹ and R ² are methyl groups, R ³ is an alkyl group having 1 to 4 carbon atoms, and R ⁴ is a hydrogen atom, methyl group, ethyl group, chloro group, bromo group Group or the following formulas (7) to (9)
It is preferable from the point that it is excellent in the availability of raw materials used in the production method described later, the ease in production, and the performance of the cured coating film when the obtained compound is used. Combinations are more preferred.

  Examples of the PFPE chain in the fluorinated acetophenone derivative (III) include those having a structure in which divalent fluorocarbon groups having 1 to 3 carbon atoms and oxygen atoms are alternately connected. The divalent fluorocarbon group having 1 to 3 carbon atoms may be one kind or a mixture of plural kinds, and specifically, those represented by the following structural formula 1 may be mentioned. Can do.

(In the structural formula 1, X is the following structural formulas a to f, and all X in the structural formula 1 may have the same structure, or a plurality of structures may be randomly or block-like. And n is a number of 1 or more representing a repeating unit.

  Among these, the perfluoromethylene structure represented by the structural formula a and the perfluoroethylene structure represented by the structure b coexist from the viewpoint of improving the scratch resistance of the cured coating obtained in particular. Is particularly preferred. Here, the abundance ratio between the perfluoromethylene structure represented by the structural formula a and the perfluoroethylene structure represented by the structure b is such that the molar ratio (structure a / structure b) is 1/4 to 4 /. A ratio of 1 is more preferable from the viewpoint of scratch resistance, and the value of n in the structural formula 1 is in the range of 3 to 40, particularly 6 to 30 is preferable.

  The PFPE chain preferably has a total of 18 to 200 fluorine atoms contained in one PFPE chain from the viewpoint of easily improving the compatibility with the non-fluorine-based active energy ray-curable compound. The range of 25 to 80 is particularly preferable. The weight average molecular weight (Mw) of the PFPE chain is preferably in the range of 400 to 10,000, more preferably 500 to 5,000.

The number average molecular weight (Mn) and the weight average molecular weight (Mw) are values converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as “GPC”) measurement. The measurement conditions for GPC are as follows.
[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” (6.0 mm ID × 4 cm) manufactured by Tosoh Corporation + “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + Tosoh Corporation manufactured by Tosoh Corporation “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + “TSK− manufactured by Tosoh Corporation” GEL GMHHR-N "(7.8 mm ID x 30 cm)
Detector: ELSD ("ELSD2000" manufactured by Oltec)
Data processing: “GPC-8020 Model II data analysis version 4.30” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min Sample: A 1.0% by mass tetrahydrofuran solution filtered in terms of resin solids through a microfilter (100 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II Data Analysis Version 4.30”.

(Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
“F-288” manufactured by Tosoh Corporation
“F-550” manufactured by Tosoh Corporation

  A in the general formula (1) is a direct bond, a divalent or trivalent linking group, a compound having a PFPE chain as described later, or a raw material-derived structure when an acryloyl group is introduced into the compound. Examples include the following linking groups.

  As described above, the fluorinated acetophenone derivative (III) has a acetophenone-like structure that functions as a Michael donor and can be split by active energy rays with respect to a PFPE chain-containing compound having an acryloyl group. It can be obtained by Michael addition reaction.

  Examples of the PFPE chain-containing compound having an acryloyl group include the following.

  In order to obtain the PFPE chain-containing compound having an acryloyl group at the terminal, for example, a method of reacting acrylic acid chloride with a compound having a hydroxyl group at the terminal of the PFPE chain, a method of dehydrating acrylic acid, -A method of urethanizing acryloyloxyethyl isocyanate, a method of urethanizing 1,1- (bisacryloyloxymethyl) ethyl isocyanate, a method obtained by esterifying itaconic anhydride, and the PFPE chain Examples include a method of esterifying 4-hydroxybutyl acrylate glycidyl ether with a compound having a carboxyl group at the end, and reacting 2-hydroxyethylacrylamide with a compound having an isocyanate group at the end of the PFPE chain. Direction And the like, with respect to further compounds having an epoxy group at the end of the PFPE chains, and a method such as reacting acrylic acid. Among these, a method obtained by reacting a compound having a hydroxyl group at the end of the PFPE chain with acrylic acid chloride, 2-acryloyloxyethyl isocyanate, and 1,1- (bisacryloyloxymethyl) ethyl isocyanate as urethane. The method obtained by the chemical reaction is particularly preferred from the viewpoint of easy reaction in production.

  A compound having a hydroxyl group at the terminal of the poly (perfluoroalkylene ether) chain, a compound having a carboxyl group at the terminal of the poly (perfluoroalkylene ether) chain, and an isocyanate group at the terminal of the poly (perfluoroalkylene ether) chain Examples of the compound and the compound having an epoxy group at the end of the poly (perfluoroalkylene ether) chain include compounds having the following structures.

In the present invention, the compound serving as the Michael donor has an acetophenone-like structure that functions as a Michael donor and can be split by active energy rays with respect to the PFPE chain-containing compound having an acryloyl group. Any compound may be used, and examples thereof include the following formulas (D1) to (D36). (In the following structural formulas, C, CH, and CH ₂ may be omitted.)

These α-aminoacetophenone derivatives can be obtained, for example, by the following method. Alkyl acetophenone (a) is synthesized by reacting a halogenated benzene with a fatty acid halide compound, then the α-position of the ketone moiety is halogenated, and then a secondary monoamine compound (HN (R ¹ ) (R ² )) Is reacted to synthesize an intermediate product (c) aminated at the α-position. Next, the benzyl bromide compound is reacted and treated with an alkali to lead to an intermediate product (d). Further, the aromatic cyclic halogen substituent is substituted with a divalent amino group-containing compound (HYH). Thus, the target α-aminoacetophenone skeleton-containing compound (f) can be produced.

In the case where a benzyl bromide compound having an ester or carboxylic acid on the aromatic ring of benzyl bromide (X ⁶ is a carbonyl group, X ⁷ is OR ¹⁰ ; R ¹⁰ is an alkyl group or hydrogen) is used as the benzyl bromide compound described above. The compound (d) having a carboxylic acid group at the terminal of the benzyl group can be synthesized by the alkali treatment, and an intermediate product is obtained by subjecting it to an amidation reaction or an esterification reaction with an amino group-containing compound or a hydroxyl group-containing compound. Next, the aromatic cyclic halogen substituent is substituted with a divalent amino group-containing compound (H—Y—H), and an amide group or ester group is contained on the aromatic ring of the benzyl group. -Aminoacetophenone skeleton-containing compound (f) can be produced.

More specifically, the above production method can be produced according to the following reaction formula, for example, taking the compound represented by the structural formula (M18) as an example. (In the following structural formulas, C, CH, and CH ₂ may be omitted.)

  That is, bromine is reacted with an acyl derivative (101) obtained by Friedel-Craft acylation reaction from fluorinated benzene and butyric acid chloride to synthesize brominated product (102), followed by dimethylamine. The bromine moiety is substituted to give a dimethylamino compound (103), which is further reacted with a benzyl bromide derivative (methyl p-bromomethylbenzoate) having an ester substituent at the 4-position to lead to a quaternary ammonium chloride, sodium hydroxide. A (104) intermediate having an α-aminoacetophenone skeleton is synthesized by a 1.2-rearrangement reaction (Stevens transfer) according to Thereafter, it is reacted with an amine such as morpholine by active esterification or acid chloride to lead to an amidated product (105), and further reacted with piperazine at 60 ° C. to 160 ° C., and the target Michael addition donor site is piperazino. A compound (M18) as a group can be produced.

Here, in the above reaction formula, R ^{1 to} R ⁴ , X ^{5 to} X ⁷ , and Y are as defined in the general formula (1), and Hal represents a halogen atom such as a fluorine atom, a bromine atom, or a chlorine atom. .

In the production method, the secondary monoamine compound (HN (R ¹ ) (R ² )) is dimethylamine, diethylamine, methylbutylamine, methyloctylamine, methyldodecylamine, ethylhexylamine, diethanolamine, 2,2′- Examples include diethoxydiethylamine, diisopropanolamine, morpholine, pyrrolidine, piperidine, N-methylpiperazine, and 2,6-dimethylmorpholine. Examples of the benzyl bromide compound having a substituent (—X ⁵ —X ⁶ —OR) on the aromatic nucleus include, for example, methyl bromomethylbenzoate, methyl 2- [4- (bromomethyl) phenyl]] propionate, 2- [4 -(Bromomethyl) phenyl]] ethyl acetate, methyl bromomethylthiobenzoate, methyl 2- [4- (bromomethyl) phenyl]] thiopropionate, and the like.

  When the fluorine-containing acetophenone derivative (III) is produced by the Michael addition reaction, the reaction is not particularly limited and can be performed under known and usual reaction conditions. As a general method, the acetophenone derivative and the PFPE chain-containing compound having an acryloyl group at the terminal may be mixed in a reaction vessel at 0 to 150 ° C., and a catalyst or a solvent can also be used.

  Usable catalysts include, for example, tetraethylammonium fluoride, tetrabutylammonium hydroxide, potassium hydroxide, tetramethylguanidi, diazabicycloundecene, sodium t-butyrate, tri-n-octylphosphine, triphenyl A phosphine etc. are mentioned.

  Examples of the organic solvent include saturated hydrocarbons such as pentane, hexane, heptane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, methanol, ethanol, isopropanol, 2-butanol, t-butanol, ethylene glycol, Alcohols such as carbitol, ethers such as dimethyl ether, diethyl ether, 1,4-dioxane and tetrahydrofuran (THF), nitrile solvents such as acetonitrile, amides such as dimethylformamide (DMF), and halogens such as chloroform and dichloromethane A solvent, dimethyl sulfoxide (DMSO), etc. can be mentioned.

  The mixing ratio of the acetophenone derivative and the PFPE chain-containing compound having an acryloyl group at the end is not particularly limited, but the number of groups having a Michael accepting function with respect to a group having a Michael donating function (Michael donating functional group / Michael The accepting functional group is preferably 10/1 to 1/10. From the viewpoint of the balance between the segregation function of the resulting fluorinated acetophenone derivative on the gas-liquid surface and the decomposition function with active energy rays, it is particularly preferably 1/2 to 2/1.

  The fluorine-containing acetophenone derivative (III) can be used alone as a so-called fluorine-based surface modifier, and by adding it to an antireflection coating composition, the surface of the resulting cured product has remarkable scratch resistance. An effect can be expressed. At this time, when the blending ratio of the fluorine-containing acetophenone derivative (III) is in the range of 0.01 to 5.0% by mass with respect to the solid content in the composition, scratch resistance and transparency of the resulting coating film are obtained. It is preferable from the point that it is excellent in balance with the property.

  When used in an antireflective coating composition, the fluorinated acetophenone derivative (III) undergoes a splitting reaction similar to that of a general photoinitiator due to the active energy rays irradiated when the composition is cured. It is firmly fixed to the other active energy ray-curable compound to be blended.

  In particular, when blended in a composition blended with a non-fluorine-based active energy ray-curable compound, the fluorine-containing acetophenone derivative (III) is a gas-liquid interface (outermost surface) of the cured product due to the surface segregation function by fluorine atoms in the PFPE chain By moving to, the active energy ray is irradiated in a concentrated state on the surface of the cured product. As a result, it is combined with other curable components on the outermost surface, PFPE chains are arranged at a high density, and remarkable antifouling properties, scratch resistance, slipping properties and the like are exhibited.

  In order to more effectively express the function inherent to such a PFPE chain, it is preferable to use another fluorine-based surfactant in combination. Other fluorosurfactants have the effect of further moving the fluorinated acetophenone derivative (III) to the surface and function as a compatibilizer between the non-fluorinated active energy ray-curable compound and the fluorinated acetophenone derivative (III). And as a result, it is thought that the bondability with the curable compound by irradiation of an active energy ray can be improved. These synergistic effects drastically improve the scratch resistance of the surface of the cured coating film.

  Examples of the fluorine-based surfactant that can be used here include a compound having a C 1-6 perfluoroalkyl group to which a fluorine atom is directly bonded, and a PFPE chain in the fluorine-containing acetophenone derivative (III). The compound which has the same PFPE chain | strand is mentioned, You may synthesize | combine or may be a commercially available thing. Examples of commercially available products include Megafax F-251, F-253, F-477, F-553, F-554, F-556, F-558, F-559, F-560, F-561, F-562, F-568, F-569, F-574, R-40, RS-75, RS-56, RS-76- E, RS-78, RS-90 [above, manufactured by DIC Corporation], Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 [above, manufactured by Asahi Glass Co., Ltd.] and the like. Among these, from the viewpoint of compatibility with the fluorine-containing acetophenone derivative (III), a surfactant having a PFPE chain is preferable, and it is difficult for the cured coating surface to fall off, and the cured coating surface has a long period. From the viewpoint of maintaining the performance, it is preferable to use the compound (IV) having a poly (perfluoroalkylene ether) chain and a polymerizable unsaturated group.

  The compound (IV) having a poly (perfluoroalkylene ether) chain and a polymerizable unsaturated group may be either synthesized or commercially available. For example, International Publication WO2009 / You may use what is provided by 133770 grade | etc.,.

  That is, as the compound (IV) having a PFPE chain and a polymerizable unsaturated group, the compound (IV-1) having a PFPE chain and a structural site having a polymerizable unsaturated group at the terminal thereof, and a reactive functional group A copolymer having the polymerizable unsaturated monomer (IV-2) having (α) as an essential raw material, and a reactive functional group (β having reactivity with the reactive functional group (α)) ) And a compound (IV-3) having a polymerizable unsaturated group.

  As the PFPE chain in the compound (IV-1) having a structural site having a polymerizable unsaturated group at the terminal thereof and the PFPE chain, divalent fluorocarbon groups having 1 to 3 carbon atoms and oxygen atoms are alternately arranged. Examples thereof include those having a linked structure, which are the same as described above.

  The compound before introducing the polymerizable unsaturated group to the terminal which is the raw material of the compound (IV-1) having the PFPE chain and the polymerizable unsaturated group is the same as described above, and has a hydroxyl group at the terminal of the PFPE chain. , Carboxy group, isocyanate, or epoxy group-containing one can be used.

  Examples of the polymerizable unsaturated group of the compound (IV-1) having a PFPE chain and a polymerizable unsaturated group include polymerizable unsaturated groups represented by the following structural formulas U-1 to U-5.

  Among these polymerizable unsaturated groups, it is easy to obtain raw materials and manufacture, or from the ease of copolymerization with a polymerizable unsaturated monomer (IV-2) having a reactive functional group (α) described later. An acryloyloxy group or a methacryloyloxy group is preferred.

  As a method for producing the compound (IV-1) having a PFPE chain and a polymerizable unsaturated group, for example, (meth) acrylic acid chloride is dehydrochlorinated with respect to a compound having a hydroxyl group at the end of the PFPE chain. A method obtained by dehydrating (meth) acrylic acid, a method obtained by urethanizing 2- (meth) acryloyloxyethyl isocyanate and 1,1- (bisacryloyloxymethyl) ethyl isocyanate, itaconic anhydride A method obtained by esterifying an acid, a method obtained by reacting styrene having a chloromethyl group with a base in the presence of a base; 4-hydroxybutyl acrylate glycidyl ether is esterified to a compound having a carboxyl group at the end of a PFPE chain Of glycidyl (meth) acrylate by esterification A method obtained by reacting; a method of introducing 2-hydroxyethyl (meth) acrylate by reacting with a compound having an isocyanate group at the end of the PFPE chain; and a method of reacting 2-hydroxyethyl (meth) acrylamide. It is done. Among these, a method in which (meth) acrylic acid chloride is dehydrochlorinated with respect to a compound having one hydroxyl group at both ends of the PFPE chain and urethanization of 2- (meth) acryloyloxyethyl isocyanate The method obtained by reacting is particularly preferable in that it can be easily obtained synthetically.

  In the present invention, “(meth) acryloyl group” means one or both of methacryloyl group and acryloyl group, “(meth) acrylate” means one or both of methacrylate and acrylate, and “(meth) “Acrylic acid” refers to one or both of methacrylic acid and acrylic acid.

  Specific examples of the compound (IV-1) having the PFPE chain and a polymerizable unsaturated group include those represented by the following structural formula. In the following structural formulas, “—PFPE—” represents a poly (perfluoroalkylene ether) chain.

  Among these, those having (meth) acryloyl groups at both ends of the PFPE chain are more preferred from the viewpoint of easy industrial production of the compound (IV).

  Examples of the polymerizable unsaturated monomer (IV-2) having the reactive functional group (α) include acrylic monomers, aromatic vinyl monomers, vinyl ester monomers, maleimide monomers. Examples thereof include those having a reactive functional group (α).

  Examples of the reactive functional group (α) include a hydroxyl group, an isocyanate group, an epoxy group, and a carboxyl group. As the polymerizable unsaturated monomer (II-2) having the reactive functional group (α), For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1, 4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy -3-phenoxypro Hydroxyl group-containing unsaturated monomers such as pill (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalate, terminal hydroxyl group-containing lactone-modified (meth) acrylate; 2- (meth) acryloyloxyethyl isocyanate, Isocyanate group-containing unsaturated monomers such as 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate; glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl Epoxy group-containing unsaturated monomers such as ether; carboxyl groups such as (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, maleic acid, itaconic acid Unsaturated Mer; maleic acid, acid anhydride having an unsaturated double bond such as itaconic anhydride.

  Further, other polymerizable unsaturated monomers that can be copolymerized with compound (IV) include methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, (meth) ) Acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid-n-heptyl, (meth) acrylic acid -N-octyl, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, etc. (Meth) acrylic acid esters of aromatic vinyl such as styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene Le acids; maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, may be used in combination maleimide and cyclohexyl maleimide.

  Here, a compound (IV-1) having a PFPE chain and a structural site having a polymerizable unsaturated group at its terminal, a polymerizable unsaturated monomer (IV-2) having a reactive functional group (α), As a method for obtaining a copolymer containing as an essential raw material, the compound (IV-1), a polymerizable unsaturated monomer (IV-2) having a reactive functional group (α), and further if necessary Examples include a method of polymerizing other polymerizable unsaturated monomers in an organic solvent using a radical polymerization initiator. As the organic solvent used here, ketones, esters, amides, sulfoxides, ethers, hydrocarbons are preferable. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These are appropriately selected in consideration of boiling point, compatibility, and polymerizability. Examples of the radical polymerization initiator include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile. Furthermore, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid and the like can be used as necessary.

  The molecular weight of the obtained copolymer needs to be in a range in which crosslinking insolubilization does not occur during polymerization, and crosslinking insolubilization may occur if the molecular weight is too high. Within that range, the copolymer has a number average molecular weight (Mn) of 800 to 3,000, particularly in that the number of polymerizable unsaturated groups in one molecule of the finally obtained compound (II) increases. It is preferably in the range of 1,000 to 2,500, and the weight average molecular weight (Mw) is preferably in the range of 1,500 to 40,000, particularly 2,000 to 30,000.

  The copolymer (IV-3) having a reactive functional group (β) and a polymerizable unsaturated group having reactivity with the reactive functional group (α) is added to the copolymer obtained as described above. The target compound (IV) is obtained by reacting.

  Examples of the reactive functional group (β) having reactivity with the reactive functional group (α) include a hydroxyl group, an isocyanate group, an epoxy group, and a carboxyl group. When the reactive functional group (α) is a hydroxyl group, examples of the functional group (β) include an isocyanate group, a carboxyl group, a carboxylic acid halide group, and an epoxy group, and the reactive functional group (α) is an isocyanate group. In this case, the functional group (β) includes a hydroxyl group, and when the reactive functional group (α) is an epoxy group, the functional group (β) includes a carboxyl group and a hydroxyl group, and the reactive functional group ( When α) is a carboxyl group, examples of the functional group (β) include an epoxy group and a hydroxyl group.

  Specifically, examples of such compound (IV-3) include those exemplified as the polymerizable unsaturated monomer (II-2) having the reactive functional group (α), and 2-hydroxy- Examples include 3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate.

  Of these, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 1,4- Cyclohexanedimethanol monoacrylate, N- (2-hydroxyethyl) acrylamide, 2-acryloyloxyethyl isocyanate, 4-hydroxybutyl acrylate glycidyl ether, and acrylic acid are preferred.

  The method of reacting compound (IV-3) with the copolymer may be carried out under the condition that the polymerizable unsaturated group in compound (IV-3) is not polymerized. For example, the temperature condition is in the range of 30 to 120 ° C. It is preferable to adjust the reaction. This reaction is preferably carried out in the presence of a catalyst or a polymerization inhibitor, and if necessary in the presence of an organic solvent.

  For example, when the functional group (α) is a hydroxyl group and the functional group (β) is an isocyanate group, or the functional group (α) is an isocyanate group and the functional group (β) is a hydroxyl group. In this case, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol or the like is used as a polymerization inhibitor, and dibutyltin dilaurate, dibutyltin diacetate, tin octylate, A method in which zinc octylate or the like is used and the reaction is performed at a reaction temperature of 40 to 120 ° C., particularly 60 to 90 ° C. is preferable. When the functional group (α) is an epoxy group and the functional group (β) is a carboxyl group, or the functional group (α) is a carboxyl group and the functional group (β) is an epoxy group. In this case, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol or the like is used as a polymerization inhibitor, and tertiary amines such as triethylamine are used as an esterification reaction catalyst. Using a quaternary ammonium such as tetramethylammonium, a tertiary phosphine such as triphenylphosphine, a quaternary phosphonium such as tetrabutylphosphonium chloride, etc., and a reaction temperature of 80 to 130 ° C., particularly 100 to 120 ° C. It is preferable to make it react with.

  The organic solvent used in the reaction is preferably ketones, esters, amides, sulfoxides, ethers or hydrocarbons. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene Examples include glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These may be appropriately selected in consideration of the boiling point and compatibility.

  The compound (IV) described in detail above preferably has a number average molecular weight (Mn) in the range of 500 to 10,000, and more preferably in the range of 1,000 to 6,000. Moreover, it is preferable that a weight average molecular weight (Mw) is the range of 3,000-80,000, and it is preferable that it is the range of 4,000-60,000. By setting Mn and Mw of the compound (IV) within these ranges, gelation can be prevented, and it becomes easy to obtain a cured coating film that is highly crosslinked and excellent in antifouling properties. Mn and Mw are values measured based on the GPC measurement described above.

  Moreover, the content rate of the fluorine atom contained in the said compound (IV) has the preferable range of 2-35 mass% from the point of the antifouling property of a cured coating film. Furthermore, content of the polymerizable unsaturated group in compound (IV) is 200-5,000 g / eq. The ratio is preferably from the viewpoint of excellent antifouling properties of the cured coating film, particularly 500 to 3,000 g / eq. It is particularly preferable that the range is

  In addition, as the compound (IV) having a PFPE chain and a polymerizable unsaturated group, for example, when a compound having an adamantyl group provided in JP 2012-92308 A is used, the surface hardness of the cured coating film is increased. Can be increased. Furthermore, the PFPE chain and the compound (IV-1) having a polymerizable unsaturated group at both ends and a polymerizable unsaturated group having a reactive functional group (α) provided in JP2011-74248A are disclosed. A copolymer obtained by copolymerizing a monomer (IV-2) as an essential monomer component, a functional group (β) reactive with the functional group (α), and two or more polymerizable properties The compound obtained by making the compound (IV-3 ') which has an unsaturated group react may be sufficient.

  Further, the blending ratio of the fluorinated acetophenone derivative (III) and the fluorosurfactant is represented by fluorinated acetophenone derivative (III) / fluorinated surfactant from the viewpoint of compatibility with the composition. The mass ratio is preferably in the range of 1/1 to 1/1000, particularly when the compound (IV) having a poly (perfluoroalkylene ether) chain and a polymerizable unsaturated group is used as the fluorosurfactant. The mass ratio of (III) / (IV) is preferably in the range of 1/5 to 1/500.

  When the antireflection coating composition of the present invention is cured by irradiating active energy rays such as ultraviolet rays, the polymerization initiator (V) is blended in the antireflection coating composition of the present invention. Examples of the polymerization initiator (V) include benzophenone, acetophenone, benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzyl methyl ketal, azobisisobutyronitrile, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2- Methyl-1-phenyl-1-one, 1- (4′-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4′-dodecylphenyl) -2-hydroxy-2-methyl Propan-1-one, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4 ″ -diethylisophthalophene, 2,2-dimethoxy-1,2-diphenylethane -1-one, benzoin isopropyl ether, thioxanthone, 2 Chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) -butanone-1, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6, -trimethylbenzoyl)- Examples thereof include phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and these may be used alone or in combination of two or more.

  Moreover, if necessary, a photosensitizer such as an amine compound or a phosphorus compound can be added to promote photopolymerization.

   The blending amount of the polymerization initiator (V) is such that the low refractive index agent (I), the active energy ray-curable compound (II) and the fluorine-containing acetophenone derivative (III), and other fluorine-based interfaces blended as necessary. It is preferably in the range of 0.01 to 15 parts by mass, more preferably in the range of 0.3 to 7 parts by mass with respect to 100 parts by mass of the total amount of the activator.

  Furthermore, the antireflective coating composition of the present invention is an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, within the range not impairing the effects of the present invention, depending on the purpose of use, characteristics, etc. Additives such as a light-resistant stabilizer stabilizer, a heat-resistant stabilizer, and an antioxidant can be blended.

  In addition, in order to impart coating suitability to the antireflection coating composition of the present invention, an organic solvent may be added to adjust the viscosity. Examples of the organic solvent that can be used here include acetate solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxypropionate; aromatics such as toluene, xylene, and methoxybenzene. Group solvents; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aliphatic hydrocarbon solvents such as hexane; N, N- Nitrogen compound solvents such as dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone; Lactone solvents such as γ-butyrolactone; Examples thereof include bamic acid esters. These solvents can be used alone or in combination of two or more.

  Here, the amount of the organic solvent used varies depending on the intended use, the desired film thickness and viscosity, but the low refractive index agent (I), the active energy ray-curable compound (II), and the fluorine-containing acetophenone derivative (III), necessary. It is preferable that the amount is in the range of 4 to 200 times on a mass basis with respect to the total of other fluorine-based surfactants blended according to the above.

  Examples of active energy rays for curing the antireflection coating composition of the present invention include active energy rays such as light, electron beam, and radiation. Specific energy sources or curing devices include, for example, germicidal lamps, ultraviolet fluorescent lamps, carbon arcs, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light, etc. Or an electron beam using a scanning type or curtain type electron beam accelerator. In addition, when making it harden | cure with an electron beam, the mixing | blending of the said polymerization initiator to the antireflection coating composition of this invention is unnecessary.

  Among these active energy rays, ultraviolet rays are particularly preferable. Further, it is preferable to irradiate in an inert gas atmosphere such as nitrogen gas since the surface curability of the coating film is improved. Further, if necessary, heat may be used as an energy source and heat treatment may be performed after curing with active energy rays.

  Examples of the application method of the antireflection coating composition of the present invention include a gravure coater, a roll coater, a comma coater, a knife coater, a curtain coater, a shower coater, a spin coater, a slit coater, dipping, screen printing, spraying, an applicator, and a bar. The coating method using a coater etc. is mentioned.

The antireflection film of the present invention has a cured coating film of the antireflection coating composition of the present invention. Specifically, the antireflection film can be produced by the following method.
(1) First, a hard coat material is applied to a substrate and cured to form a hard coat layer coating.
(2) The antireflective coating composition of the present invention is applied to the hard coat layer and cured to form a coating film having a low refractive index layer. This low refractive index layer becomes the outermost surface of the antireflection film.
A medium refractive index layer and / or a high refractive index layer may be provided between the hard coat layer and the low refractive index layer.

  The hard coat material can be used without particular limitation as long as a cured coating film having a relatively high surface hardness can be obtained, but the active energy ray curable exemplified as the active energy ray curable compound (II). A combination of the monomer (II-1) and the active energy ray-curable resin (II-2) is preferable.

  The thickness of the hard coat layer is preferably in the range of 0.1 to 100 μm, more preferably in the range of 1 to 30 μm, and still more preferably in the range of 3 to 15 μm. When the thickness of the hard coat layer is within this range, the adhesion to the substrate and the surface hardness of the antireflection film are increased. Further, the refractive index of the hard coat layer is not particularly limited. However, when the refractive index is high, good antireflection can be achieved without providing the medium refractive index layer and the high refractive index layer.

  The thickness of the low refractive index layer formed by applying and curing the antireflection coating composition of the present invention is preferably in the range of 50 to 300 nm, more preferably in the range of 50 to 150 nm, and 80 to More preferably, it is in the range of 120 nm. When the thickness of the low refractive index layer is within this range, the antireflection effect can be improved. In addition, the refractive index of the low refractive index layer is preferably in the range of 1.20 to 1.45, and more preferably in the range of 1.23 to 1.42. When the refractive index of the low refractive index layer is within this range, the antireflection effect can be improved.

  The thickness of the medium refractive index layer or the high refractive index layer is preferably in the range of 10 to 300 nm, and more preferably in the range of 30 to 200 nm. Further, the refractive index of the medium refractive index layer or the high refractive index layer is selected depending on the refractive indexes of the low refractive index layer and the hard coat layer existing above and below, but is arbitrarily selected within the range of 1.40 to 2.00. Can be set.

  Examples of the material for forming the medium refractive index layer or the high refractive index layer include epoxy resins, phenol resins, melamine resins, alkyd resins, cyanate resins, acrylic resins, polyester resins, Resins that can be cured by heat, ultraviolet curing, and electron beam, such as urethane resins and siloxane resins. These resins can be used alone or in combination of two or more. Moreover, it is more preferable to mix inorganic fine particles having a high refractive index with these resins.

  As the high refractive index inorganic fine particles, those having a refractive index of 1.65 to 2.00 are preferable. For example, zinc oxide having a refractive index of 1.90, titania having a refractive index of 2.3 to 2.7, Ceria having a refractive index of 1.95, tin-doped indium oxide having a refractive index of 1.95 to 2.00, antimony-doped tin oxide having a refractive index of 1.75 to 1.85, a refractive index of 1.87 And yttria, and zirconia having a refractive index of 2.10. These high refractive index inorganic fine particles can be used alone or in combination of two or more.

  In addition, since the productivity can be improved by making the medium refractive index layer or the high refractive index layer the same as the antireflective coating composition of the present invention, the antireflective coating composition of the present invention can be improved. When the product is cured with ultraviolet rays, it is preferable that the ultraviolet curable composition is used to form a medium refractive index layer or a high refractive index layer.

  Examples of the substrate used for the antireflection film of the present invention include, for example, polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin films such as polypropylene, polyethylene, and polymethylpentene-1; triacetyl cellulose (TAC) Cellulose film such as polystyrene film, polyamide film, polycarbonate film, norbornene resin film (for example, “ZEONOR” manufactured by ZEON CORPORATION), modified norbornene resin film (for example, “ARTON” manufactured by JSR Corporation), Examples include cyclic olefin copolymer films (for example, “Appel” manufactured by Mitsui Chemicals, Inc.), acrylic films such as polymethyl methacrylate (PMMA), and the like. Lum may be used by laminating two or more. Further, these films may be a sheet-like. The thickness of the film substrate, 20 to 500 [mu] m is preferred.

  The reflectance of the antireflection film of the present invention is preferably 2.0% or less, more preferably 1.5% or less, and further preferably 1.0% or less.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples.

^[1 H-NMR measurement conditions]
Apparatus: JEOL Ltd. FT-NMR
JNM-ECM400S (400MHz)
Measuring solvent: deuterated chloroform (CDCl ₃ -d1)
Internal standard: Tetramethylsilane (TMS)

(Synthesis of Michael addition donor)
Below, the synthesis example of the Michael addition donor which is an alpha-aminoacetophenone derivative is described.

  Synthesis Example 1: Synthesis of compound (D1)

  A 1 L four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, alkali trap and dropping funnel was charged with 121.8 g of aluminum chloride (anhydrous) and 300 mL of dehydrated dichloromethane, and using an ice bath under a nitrogen stream. Ice-cooled. To this was added 92.7 g of butyryl chloride. A mixed solution of 83.6 g of fluorobenzene and 100 mL of dehydrated dichloromethane was dropped into the previous flask using a dropping funnel over 20 minutes. After completion of the dropping, the ice bath was removed, and the mixture was stirred as it was for 2 hours to complete the reaction. The reaction solution was poured into 1 L of ice water and stirring was continued for 2 hours. After standing, liquid separation was performed, and the lower layer was collected. Washed twice with 2N hydrochloric acid, washed once with saturated aqueous sodium hydrogen carbonate solution, and washed twice with saturated brine. After drying overnight with magnesium sulfate, dichloromethane was distilled off under reduced pressure to obtain an intermediate product (101). Yield: 144.5 g, Yield: 100%

  Into a 5 L four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, alkali trap and dropping funnel was charged 989 g of the intermediate product (101), 1500 mL of dehydrated dichloromethane, and 125 mL of acetic acid. 1000g was dripped at 20-30 degreeC, and was made to react for 1 hour. After completion of the reaction, the reaction mixture was neutralized with 8M sodium hydroxide, washed twice with water, and further washed once with saturated brine. After drying overnight with magnesium sulfate, dichloromethane was distilled off under reduced pressure to obtain an intermediate product (102). Yield: 1459 g, Yield: 100%

  A 3 L four-necked flask equipped with a stirrer and a thermometer was charged with 402 g of a 50% dimethylamine aqueous solution and 1000 mL of methyl ethyl ketone, and ice-cooled using an ice bath. Thereto, 490 g of the intermediate product (102) was added dropwise using a dropping funnel over 30 minutes. After completion of the dropwise addition, the ice bath was removed and stirring was continued for a whole day and night. After completion of the stirring, methyl ethyl ketone was distilled off under reduced pressure, and the concentrated residue was extracted with toluene. Washing was performed twice with water and once with saturated saline, and the toluene layer was dried with magnesium sulfate all day and night. Toluene was distilled off under reduced pressure to obtain a light yellow liquid intermediate product (103). Yield: 402 g, yield: 96%

  Into a 3 L four-necked flask equipped with a stirrer, a thermometer, and a condenser tube were charged 209 g of the intermediate product (103) and 400 mL of methyl ethyl ketone, and 205 g of benzyl bromide were added dropwise and stirred at 40 ° C. for 2 hours. Next, 188 mL of 8M sodium hydroxide aqueous solution was added, and it stirred at 50 degreeC for 2 hours. The reaction solution was washed three times with water and once with saturated aqueous sodium chloride, and the organic layer was dried with magnesium sulfate all day and night. Methyl ethyl ketone was distilled off under reduced pressure, and the resulting concentrated residue was recrystallized from methanol to obtain a light yellow crystal intermediate product (106). Yield: 254 g, Yield: 85%

  To a 500 mL four-necked flask equipped with a stirrer and a thermometer, 30.0 g of the intermediate product (106) and 25.8 g of anhydrous piperazine were added and heated at 120 ° C. for 15 hours under a nitrogen atmosphere. After completion, distilled water was added to stop the reaction, and the mixture was extracted with dichloromethane. The organic layer was washed with water three times and once with saturated aqueous sodium chloride, and the organic layer was dried overnight with magnesium sulfate. Dichloromethane was distilled off under reduced pressure to obtain a yellow oily Michael donor product (D1). Yield: 36.5 g, Yield: 100%

Synthesis Example 2: Synthesis of Compound (D2) According to the method described in Synthesis Example 1 except that 222 g of α-bromo-p-xylene was used instead of 205 g of benzyl bromide in Synthesis Example 1, Michael donation as a yellow oil The body product (D2) was synthesized.

Synthesis Example 3: Synthesis of Compound (D9) According to the method described in Synthesis Example 1 except that 300 g of 4-bromobenzyl bromide was used instead of 205 g of benzyl bromide in Synthesis Example 1, a yellow oily Michael donor was produced. A product (D9) was synthesized.

Synthesis Example 4: Synthesis of Compound (D16) According to the method described in Synthesis Example 1, except that 26.4 g of N, N′-dimethylethylenediamine was used instead of 25.8 g of anhydrous piperazine in Synthesis Example 1, An oily Michael donor product (D16) was synthesized.

Synthesis Example 5: Synthesis of Compound (D17) According to the method described in Synthesis Example 1 except that methyldodecylamine was used instead of 50% aqueous dimethylamine in Synthesis Example 1, a yellow oily Michael donor product (D16 ) Was synthesized.

  Synthesis Example 6 Synthesis of Compound (D18)

  A 500 mL four-necked flask equipped with a stirrer, a thermometer, and a condenser tube was charged with 27.5 g of methyl α-bromomethylbenzoate and 40 mL of isopropyl alcohol, and 20 of the intermediate product (103) synthesized in Synthesis Example 1 was obtained. 9 g was added and stirred at 40 ° C. for 2 hours. Next, 31 mL of 8M aqueous sodium hydroxide solution was added and stirred at 50 ° C. for 2 hours. Isopropyl alcohol was distilled off under reduced pressure, and the remaining reaction mixture was adjusted to pH 5 with 6N hydrochloric acid. Extraction was performed with toluene, washing with water twice and washing with a saturated saline solution were performed, and the organic layer was dried with magnesium sulfate all day and night. The organic solvent was distilled off under reduced pressure, and the resulting concentrated residue was recrystallized from ethyl acetate and hexane to obtain an intermediate product (107) as a pale yellow powder. Yield: 27.8 g, Yield: 81%

  In a 200 mL flask equipped with a stirrer, thermometer and dropping funnel, 3.43 g of the intermediate product (107), 0.1 mL of N, N-dimethylformamide (DMF) and 15 mL of methylene chloride were added and dissolved. 1.79 g of thionyl chloride was added dropwise to the reaction mixture for 2 hours. The reaction solution was concentrated under reduced pressure, and the concentrated residue was dissolved in 30 mL of dichloromethane to prepare a solution of acid chloride in dichloromethane. In another 300 mL flask equipped with a stirrer, a thermometer, and a dropping funnel, 2 mL of morpholine and 30 mL of methylene chloride were added and dissolved, and the above dichloromethane solution of acid chloride was added dropwise thereto over 20 minutes. The reaction was completed by stirring for 30 minutes, and 1M-aqueous sodium hydroxide solution was added to stop the reaction. The reaction solution was transferred to a separatory funnel, and the organic layer was washed twice with water, and then dried with magnesium sulfate all day and night. Dichloromethane was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to obtain a yellow oily intermediate product (108). Yield: 3.22 g, Yield: 78%

  To a 50 mL three-necked flask equipped with a stirrer and a thermometer, 2.06 g of the intermediate product (108) and 1.29 g of anhydrous piperazine were added and heated at 120 ° C. for 15 hours under a nitrogen atmosphere. After completion, distilled water was added to stop the reaction, and the mixture was extracted with dichloromethane. The organic layer was washed with water three times and once with saturated aqueous sodium chloride, and the organic layer was dried overnight with magnesium sulfate. Dichloromethane was distilled off under reduced pressure to obtain a yellow oily Michael donor product (D18). Yield: 2.39 g, Yield: 100%

Synthesis Example 7 Synthesis of Compound (D20) A yellow oily Michael donor product (D20) was synthesized according to the method described in Synthesis Example 6 except that dioctylamine was used instead of morpholine in Synthesis Example 6.

  Synthesis Example 8: Synthesis of compound (D23)

  A 500 mL four-necked flask equipped with a stirrer, a thermometer, and a condenser tube was charged with 29.2 g of 2- [4- (bromomethyl) phenyl] propionic acid and 40 mL of isopropyl alcohol. 15 mL was added and stirred at the same temperature for 30 minutes. 20.9 g of the intermediate product (103) synthesized in Synthesis Example 1 was added and stirred at 20 ° C. for 3 hours. Next, 22 mL of 8M aqueous sodium hydroxide solution was added and stirred at 50 ° C. for 2 hours. Isopropyl alcohol was distilled off under reduced pressure, and the remaining reaction mixture was adjusted to pH 5 with 6N hydrochloric acid. Extraction was performed with toluene, washing with water twice and washing with a saturated saline solution were performed, and the organic layer was dried with magnesium sulfate all day and night. The organic solvent was distilled off under reduced pressure, and the resulting concentrated residue was purified by silica gel column chromatography to obtain a yellow oily intermediate product (109). Yield: 24.1 g, Yield: 65%

  In a 200 mL flask equipped with a stirrer, thermometer and dropping funnel, 3.71 g of intermediate product (109), 0.1 mL of N, N-dimethylformamide (DMF) and 15 mL of methylene chloride were added and dissolved. 1.79 g of thionyl chloride was added dropwise to the reaction mixture for 2 hours. The reaction solution was concentrated under reduced pressure, and the concentrated residue was dissolved in 30 mL of dichloromethane to prepare a solution of acid chloride in dichloromethane. In another 300 mL flask equipped with a stirrer, a thermometer, and a dropping funnel, 2 mL of morpholine and 30 mL of methylene chloride were added and dissolved, and the above dichloromethane solution of acid chloride was added dropwise thereto over 20 minutes. The reaction was completed by stirring for 30 minutes, and 1M-aqueous sodium hydroxide solution was added to stop the reaction. The reaction solution was transferred to a separatory funnel, and the organic layer was washed twice with water, and then dried with magnesium sulfate all day and night. Dichloromethane was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to obtain a yellow oily intermediate product (110). Yield: 3.65 g, Yield: 83%

  2.20 g of the intermediate product (108) and 1.29 g of anhydrous piperazine were added to a 50 mL three-necked flask equipped with a stirrer and a thermometer, and heated at 120 ° C. for 15 hours under a nitrogen atmosphere. After completion, distilled water was added to stop the reaction, and the mixture was extracted with dichloromethane. The organic layer was washed with water three times and once with saturated aqueous sodium chloride, and the organic layer was dried overnight with magnesium sulfate. Dichloromethane was distilled off under reduced pressure to obtain a yellow oily Michael donor product (D23). Yield: 2.53 g, Yield: 100%

Synthesis Example 9 Synthesis of Compound (D24) A yellow oily Michael donor product (D24) was synthesized according to the method described in Synthesis Example 8 except that dioctylamine was used instead of morpholine in Synthesis Example 8.

[Synthesis of Michael addition receptor]
Below, the synthesis | combination of the Michael addition acceptor which has an acrylate group which functions as a Michael addition acceptance site at both ends of a perfluoropolyether (PFPE) group is illustrated.

Synthesis Example 10
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, a hydroxyl group-containing perfluoropolyether compound 20 g represented by the following structural formula (A-1), diisopropyl ether 20 g as a solvent, a polymerization inhibitor P-methoxyphenol 0.02 g and triethylamine 3.1 g as a neutralizer were added, stirring was started in an air stream, and 2.7 g of acrylic acid chloride was added dropwise over 1 hour while maintaining the flask at 10 ° C. did. After completion of dropping, the mixture is stirred at 10 ° C. for 1 hour, heated to 30 ° C. for 1 hour, then heated to 50 ° C. and stirred for 10 hours, and acrylic acid is measured by gas chromatography. The disappearance of chloride was confirmed. Next, after adding 40 g of diisopropyl ether as a solvent, 80 g of ion-exchanged water was mixed and stirred, and then allowed to stand, and washing by a method of separating and removing the aqueous layer was repeated three times. Next, 0.02 g of p-methoxyphenol was added as a polymerization inhibitor, 8 g of magnesium sulfate was added as a dehydrating agent, and the mixture was allowed to stand for 1 day for complete dehydration, and then the dehydrating agent was filtered off.

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups are present per molecule, and the number of fluorine atoms is (The average is 46. The number average molecular weight by GPC is 1,500.)

  Subsequently, the solvent was distilled off under reduced pressure to obtain a Michael addition acceptor having a poly (perfluoroalkylene ether) chain represented by the following structural formula (A-2).

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups are present per molecule, and the number of fluorine atoms is (The average is 46.)

Synthesis Example 11
1,3-bis (trifluoromethyl) benzene 55.88 g in a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, hydroxyl group-containing perfluoropolyester represented by the following structural formula (A-3) 50 g of ether compound, 0.022 g of p-methoxyphenol, 0.168 g of dibutylhydroxytoluene, and 0.017 g of tin octylate were charged, and stirring was started under an air stream. 1,1- (bisacryloyloxy was maintained at 75 ° C. 5.87 g of methyl) ethyl isocyanate was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 75 ° C. for 1 hour, heated to 80 ° C. and stirred for 10 hours, and the disappearance of isocyanate groups was confirmed by IR spectrum measurement.

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and an average of 19 perfluoromethylene groups and an average of 19 perfluoroethylene groups are present per molecule, and the number of fluorine atoms is (The average is 114.)

  The organic solvent was distilled off under reduced pressure to obtain a Michael addition acceptor having a poly (perfluoroalkylene ether) chain represented by the following structural formula (A-4).

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and an average of 19 perfluoromethylene groups and an average of 19 perfluoroethylene groups are present per molecule, and the number of fluorine atoms is (The average is 114.)

Synthesis Example 12
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 53.57 g of 1,3-bis (trifluoromethyl) benzene and a hydroxyl group containing one terminal hydroxyl group represented by the following structural formula (A-5) 50 g of fluoropolyether compound, 0.021 g of p-methoxyphenol, 0.161 g of dibutylhydroxytoluene, 0.016 g of tin octylate, and 3.1 g of triethylamine as a neutralizing agent were added, and stirring was started under an air stream. While maintaining the temperature at 10 ° C., 1.40 g of acrylic acid chloride was added dropwise over 1 hour. After completion of dropping, the mixture is stirred at 10 ° C. for 1 hour, heated to 30 ° C. for 1 hour, then heated to 50 ° C. and stirred for 10 hours, and acrylic acid is measured by gas chromatography. The disappearance of chloride was confirmed. Next, after adding 40 g of diisopropyl ether as a solvent, 80 g of ion-exchanged water was mixed and stirred, and then allowed to stand, and washing by a method of separating and removing the aqueous layer was repeated three times. Next, 0.02 g of p-methoxyphenol was added as a polymerization inhibitor, 8 g of magnesium sulfate was added as a dehydrating agent, and the mixture was allowed to stand for 1 day for complete dehydration, and then the dehydrating agent was filtered off.

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and there are an average of 18 perfluoromethylene groups and an average of 21 perfluoroethylene groups per molecule, and the number of fluorine atoms is (The average is 120.)

  Subsequently, the solvent was distilled off under reduced pressure to obtain a Michael addition acceptor having a poly (perfluoroalkylene ether) chain represented by the following structural formula (A-6).

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and there are an average of 18 perfluoromethylene groups and an average of 21 perfluoroethylene groups per molecule, and the number of fluorine atoms is (The average is 120.)

Synthesis Example 13
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 53.57 g of 1,3-bis (trifluoromethyl) benzene and a single-terminal hydroxyl group-containing perfluoro represented by the structural formula (A-5) First, 50 g of a polyether compound, 0.021 g of p-methoxyphenol, 0.161 g of dibutylhydroxytoluene, and 0.016 g of tin octylate were charged, and stirring was started in an air stream, and 1.1- (bisacryloyl was maintained while maintaining 75 ° C. 3.57 g of oxymethyl) ethyl isocyanate was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 75 ° C. for 1 hour, heated to 80 ° C. and stirred for 10 hours, and the disappearance of isocyanate groups was confirmed by IR spectrum measurement.

  Subsequently, the solvent was distilled off under reduced pressure to obtain a Michael addition acceptor having a poly (perfluoroalkylene ether) chain represented by the following structural formula (A-7).

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and there are an average of 18 perfluoromethylene groups and an average of 21 perfluoroethylene groups per molecule, and the number of fluorine atoms is (The average is 120.)

[Synthesis of Michael adduct]
Hereinafter, the synthesis of a Michael adduct synthesized from a Michael addition donor having an α-aminoacetophenone structure and a Michael addition acceptor having a perfluoropolyether (PFPE) group is exemplified.

Synthesis Example 14
15.0 g of the Michael addition acceptor (A-2) synthesized in Synthesis Example 10 in a 100 mL three-necked flask equipped with a stirrer, a condenser and a thermocouple, and the Michael addition donor (D1) 7 obtained in Synthesis Example 1 .3 g and 15 mL of acetonitrile were added and stirred at room temperature for 24 hours. The reaction mixture was concentrated under reduced pressure to obtain 22.3 g of a fluorine-containing acetophenone derivative [the above compound (M1)]. A ¹ H-NMR chart of the compound (M1) is shown in FIG.

Synthesis Example 15
15.0 g of Michael addition acceptor (A-2) synthesized in Synthesis Example 10 in a 100 mL three-necked flask equipped with a stirrer, condenser and thermocouple, and Michael addition donor (D2) 7 obtained in Synthesis Example 2 .6 g and 15 mL of acetonitrile were added, and the mixture was stirred at room temperature for 24 hours. The reaction mixture was concentrated under reduced pressure to obtain 22.6 g of a fluorine-containing acetophenone derivative [the above compound (M2)]. A ¹ H-NMR chart of the compound (M2) is shown in FIG.

Synthesis Example 16
15.0 g of the Michael addition acceptor (A-2) synthesized in Synthesis Example 10 in a 100 mL three-necked flask equipped with a stirrer, a condenser and a thermocouple, and the Michael addition donor (D9) 8 obtained in Synthesis Example 3 .9 g and 15 mL of acetonitrile were added and stirred at room temperature for 24 hours. The reaction mixture was concentrated under reduced pressure to obtain 23.9 g of a fluorine-containing acetophenone derivative [the aforementioned compound (M9)]. A ¹ H-NMR chart of the compound (M9) is shown in FIG.

Synthesis Example 17
15.0 g of Michael addition acceptor (A-2) synthesized in Synthesis Example 10 in a 100 mL three-necked flask equipped with a stirrer, a condenser and a thermocouple, and Michael addition donor (D16) 7 obtained in Synthesis Example 4 .4 g and 15 mL of acetonitrile were added and stirred at room temperature for 24 hours. The reaction mixture was concentrated under reduced pressure to obtain 22.4 g of a fluorine-containing acetophenone derivative [the above compound (M16)].

Synthesis Example 18
15.0 g of the Michael addition acceptor (A-2) synthesized in Synthesis Example 10 in a 100 mL three-necked flask equipped with a stirrer, a condenser and a thermocouple, and the Michael addition donor (D17) 10 obtained in Synthesis Example 5 .4 g and 15 mL of acetonitrile were added and stirred at room temperature for 24 hours. The reaction mixture was concentrated under reduced pressure to obtain 25.4 g of a fluorine-containing acetophenone derivative [the above compound (M17)].

Synthesis Example 19
15.0 g of the Michael addition acceptor (A-2) synthesized in Synthesis Example 10 in a 100 mL three-necked flask equipped with a stirrer, a condenser and a thermocouple, and Michael addition donor (D18) 9 obtained in Synthesis Example 6 .6 g and 15 mL of acetonitrile were added, and the mixture was stirred at room temperature for 24 hours. The reaction mixture was concentrated under reduced pressure to obtain 24.6 g of a fluorine-containing acetophenone derivative [the above compound (M18)]. A ¹ H-NMR chart of the compound (M18) is shown in FIG.

Synthesis Example 20
15.0 g of Michael addition acceptor (A-2) synthesized in Synthesis Example 10 in a 100 mL three-necked flask equipped with a stirrer, condenser and thermocouple, and Michael addition donor (D20) 12 obtained in Synthesis Example 7 .6 g and 15 mL of acetonitrile were added, and the mixture was stirred at room temperature for 24 hours. The reaction mixture was concentrated under reduced pressure to obtain 27.6 g of a fluorine-containing acetophenone derivative [the above compound (M20)]. A ¹ H-NMR chart of the compound (M20) is shown in FIG.

Synthesis Example 21
15.0 g of Michael addition acceptor (A-2) synthesized in Synthesis Example 10 in a 100 mL three-necked flask equipped with a stirrer, a condenser and a thermocouple, and Michael addition donor (D23) 10 obtained in Synthesis Example 8 0.1 g and 15 mL of acetonitrile were added and stirred at room temperature for 24 hours. The reaction mixture was concentrated under reduced pressure to obtain 25.1 g of a fluorine-containing acetophenone derivative [the aforementioned compound (M23)].

Synthesis Example 22
15.0 g of Michael addition acceptor (A-2) synthesized in Synthesis Example 10 in a 100 mL three-necked flask equipped with a stirrer, a condenser and a thermocouple, and Michael addition donor (D24) 13 obtained in Synthesis Example 9 0.2 g and 15 mL of acetonitrile were added and stirred at room temperature for 24 hours. The reaction mixture was concentrated under reduced pressure to obtain 28.2 g of a fluorine-containing acetophenone derivative [the aforementioned compound (M24)].

Synthesis Example 23
45.0 g of the Michael addition acceptor (A-4) synthesized in Synthesis Example 11 in a 300 mL three-necked flask equipped with a stirrer, a condenser and a thermocouple, and the Michael addition donor (D1) 14 obtained in Synthesis Example 1 .6 g and 100 mL of acetonitrile were added and stirred at room temperature for 24 hours. The reaction mixture was concentrated under reduced pressure to obtain 59.6 g of a fluorine-containing acetophenone derivative [the above compound (M37)].

Synthesis Example 24
15.0 g of Michael addition acceptor (A-4) synthesized in Synthesis Example 11 in a 200 mL three-necked flask equipped with a stirrer, a condenser and a thermocouple, and Michael addition donor (D2) 5 obtained in Synthesis Example 2 0.1 g and 50 mL of acetonitrile were added and stirred at room temperature for 24 hours. The reaction mixture was concentrated under reduced pressure to obtain 20.1 g of a fluorine-containing acetophenone derivative [the above compound (M38)].

Synthesis Example 25
13.1 g of Michael addition acceptor (A-6) synthesized in Synthesis Example 12 in a 100 mL three-necked flask equipped with a stirrer, a condenser and a thermocouple, and Michael addition donor (D1) 1 obtained in Synthesis Example 1 0.5 g and 15 mL of acetonitrile were added and stirred at room temperature for 24 hours. The reaction mixture was concentrated under reduced pressure to obtain 14.6 g of a fluorine-containing acetophenone derivative [the above compound (M60)].

Synthesis Example 26
50.0 g of Michael addition acceptor (A-7) synthesized in Synthesis Example 13 in a 300 mL three-necked flask equipped with a stirrer, condenser and thermocouple, and Michael addition donor (D1) 10 obtained in Synthesis Example 1 0.1 g and 100 mL of acetonitrile were added and stirred at room temperature for 24 hours. The reaction mixture was concentrated under reduced pressure to obtain 60.1 g of a fluorine-containing acetophenone derivative [the above compound (M96)].

Synthesis Example 27: Synthesis of Fluorosurfactant (1) A glass flask equipped with a stirrer, a thermometer, and a cooling tube has 26.4 g of isopropyl ether as a solvent and a hydroxyl group at one end represented by the following formula. 25.2 g of a silicone compound and 0.66 g of triethylamine were charged as a catalyst, and the mixture was stirred for 30 minutes while maintaining the temperature in the flask at 5 ° C.

  Next, 1.50 g of 2-bromoisobutyric acid bromide was added and stirred for 3 hours, heated to 40 ° C. and stirred for 8 hours. After completion of the reaction, 80 g of ion-exchanged water was mixed and stirred, and then left to stand, and washing by a method of separating and removing the aqueous layer was repeated three times. Next, 8 g of magnesium sulfate was added as a dehydrating agent and left to stand for 1 day for complete dehydration, and then the dehydrating agent was filtered off. Thereafter, the solvent was distilled off under reduced pressure to obtain a compound containing a functional group having a radical generating ability represented by the following formula and one silicone chain having a molecular weight of 2,000 or more.

  A nitrogen introducing tube, a stirrer, a thermometer, and a cooling tube are provided, and nitrogen-substituted glass flask is charged with 30.70 g of isopropyl alcohol, 30.70 g of methyl ethyl ketone, 10.93 g of tridecafluorohexyl ethyl methacrylate, and 0.5470 g of methoxybenzene. It stirred at 25 degreeC for 1 hour, stirring under airflow. Next, 0.4510 g of cuprous chloride, 0.1130 g of cupric bromide, and 1.581 g of 2,2-bipyridyl were charged and stirred for 30 minutes. After raising the temperature to 60 ° C., 30 g of a compound containing the functional group having radical generating ability and one silicone chain having a molecular weight of 2,000 or more was added, and the mixture was stirred for 4 hours while maintaining the temperature in the flask at 60 ° C. Then, 6.585 g of 2-hydroxyethyl methacrylate was charged and stirred for 1 hour. Thereafter, the temperature was raised to 75 ° C. and stirred for 31 hours. Under air, 1.167 g of 85% aqueous phosphoric acid solution was added and stirred for 2 hours, and the precipitated solid was separated by filtration. The catalyst was removed with an ion exchange resin, and the ion exchange resin was filtered off to obtain a block copolymer. Next, 32.54 g of the obtained copolymer, 36.70 g of methyl isobutyl ketone, and p-methoxyphenol 0 as a polymerization inhibitor were added to a glass flask equipped with a nitrogen introducing tube, a stirring device, a thermometer, a cooling tube, and a dropping device. .0149 parts by mass, 0.1116 g of dibutylhydroxytoluene and 0.0111 g of tin octylate as a urethanization catalyst were added, stirring was started under an air stream, and 4.67 g of 2-acryloyloxyethyl isocyanate was maintained while maintaining 60 ° C. added. Then, after stirring at 60 ° C. for 1 hour, the temperature was raised to 80 ° C. and stirred for 4 hours, thereby confirming the disappearance of the isocyanate group by IR spectrum measurement, and adding 50.46 g of methyl isobutyl ketone to cure the active energy ray. A methyl isobutyl ketone solution containing 30% by mass of a fluorosurfactant having a functional group was obtained. As a result of measuring the molecular weight of the obtained fluorosurfactant by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 10,500 and the weight average molecular weight was 12,000.

Synthesis Example 28: Synthesis of fluorinated surfactant (2) A glass flask equipped with a stirrer, a thermometer, a condenser tube, and a dropping device was charged with 63 g of methyl isobutyl ketone and heated to 105 ° C while stirring under a nitrogen stream. The temperature rose. Subsequently, 21.5 g of diacrylate body (A-2) synthesized in Synthesis Example 10 having a poly (perfluoroalkylene ether) chain, 41.3 g of 2-hydroxyethyl methacrylate, t-butylperoxy- as a radical polymerization initiator Three types of dripping liquid of 135.4 g of initiator solution in which 9.4 g of 2-ethylhexanoate and 126 g of methyl isobutyl ketone were mixed were set in separate dripping apparatuses, respectively, and kept at 105 ° C. for 2 hours at the same time. It was dripped over. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain 67.5 g of a polymer (P-1). Next, 74.7 g of methyl ethyl ketone as a solvent, 0.1 g of p-methoxyphenol as a polymerization inhibitor, and 0.06 g of dibutyltin dilaurate as a urethanization catalyst were charged, stirring was started in an air stream, 44.8 g of acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours. As a result, the disappearance of the isocyanate group was confirmed by IR spectrum measurement. Next, 37.4 g of methyl ethyl ketone was added to obtain 224.6 g of a methyl ethyl ketone solution containing 50% of a fluorosurfactant (2) having a PFPE chain and a polymerizable unsaturated group. As a result of measuring molecular weight by GPC (polystyrene conversion molecular weight), it was number average molecular weight 2,400, weight average molecular weight 7,100, and maximum molecular weight 200,000.

Synthesis Example 29: Synthesis of Fluorosurfactant (3) A glass flask equipped with a stirrer, a thermometer, a condenser tube, and a dropping device was charged with 74.2 parts by mass of methyl isobutyl ketone as a solvent under a nitrogen stream. The temperature was raised to 90 ° C. with stirring. Next, 9 parts by mass of tridecafluorohexylethyl methacrylate, a monomer solution in which 36 parts by mass of the monomer represented below and 26.4 parts by mass of 2-hydroxyethyl methacrylate were dissolved in 128.9 parts by mass of methyl isobutyl ketone, As a radical polymerization initiator, two kinds of dropwise addition liquids, each containing 10.7 parts by mass of t-butylperoxy-2-ethylhexanoate and 11.6 parts by mass of methyl isobutyl ketone, were separately added dropwise. It set to the apparatus and it was dripped over 2 hours simultaneously, keeping the inside of a flask at 90 degreeC. After completion of dropping, the mixture was stirred at 90 ° C. for 13 hours to obtain a polymer (P-2) solution.

  A solution of the above polymer (P-2) was charged with 0.04 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 parts by mass of tin octylate as a urethanization catalyst, and stirring was started under an air stream. While maintaining the temperature at 60 ° C., 27.7 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 10 hours, whereby disappearance of the isocyanate group was confirmed by IR spectrum measurement. Subsequently, methyl isobutyl ketone was added to obtain a methyl isobutyl ketone solution containing 20% by mass of the fluorosurfactant (3). The molecular weight of the obtained fluorosurfactant (3) was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 2,400, the weight average molecular weight was 6,400, and the polymerizable unsaturated group equivalent was 493 g / eq. Met.

Synthesis Example 30: Synthesis of fluorinated surfactant (4) 96.7 g of methyl isobutyl ketone as a solvent was placed in a glass flask equipped with a stirrer, a thermometer, a condenser tube, and a dropping device, and stirred under a nitrogen stream. The temperature was raised to 105 ° C. Next, 74 g of the compound (A-2) obtained in Synthesis Example 10, 37 g of the polymerizable unsaturated monomer having a silicone group represented by Chemical Formula 71 and 45.4 g of 2-hydroxyethyl methacrylate were added to 126 g of methyl isobutyl ketone. Three types of dripping liquids, a monomer solution dissolved in 1 and a polymerization initiator solution in which 23.5 g of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator were dissolved in 67.8 g of methyl isobutyl ketone, were separately prepared. Were added dropwise over 2 hours while keeping the inside of the flask at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours to obtain a polymer (P-3) solution. A solution of the above polymer (P-3) was charged with 0.2 g of p-methoxyphenol as a polymerization inhibitor and 0.06 g of tin octylate as a urethanization catalyst, and stirring was started in an air stream. While maintaining, 49.1 g of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 60 ° C. for 1 hour, heated to 80 ° C. and stirred for 10 hours, and disappearance of isocyanate groups was confirmed by IR spectrum measurement. Subsequently, methyl isobutyl ketone was added to obtain a methyl isobutyl ketone solution containing 40% of the fluorosurfactant (4). As a result of measuring the molecular weight of the obtained fluorosurfactant (4) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,700, the weight average molecular weight was 8,000, and the polymerizable unsaturated group equivalent was 588 g / eq. Met.

<Adjustment of antireflection coating composition>
15 parts by mass of a methyl isobutyl ketone dispersion containing 20% by mass of hollow silica fine particles (average particle diameter 60 nm), 1.6 parts by mass of pentaerythritol triacrylate, and 2-hydroxy-1- {4- [4 as a photopolymerization initiator 0.1 part by mass of-(2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one ("Irgacure 127" manufactured by Ciba Japan Co., Ltd.), methyl isobutyl as a solvent 100 parts by mass of ketone was mixed and dissolved to obtain a base composition of an antireflection coating composition. 1.6 parts by mass of a fluorosurfactant and 9% by mass of the fluorine-containing acetophenone derivative shown in the table are added to 98.5 parts by mass of the base composition of the antireflective coating composition obtained above, and mixed uniformly. The antireflection coating composition of the present invention was prepared.

<Composition of coating composition for hard coat layer>
30 parts by mass of urethane acrylate (“UV1700B” from Nippon Synthetic Chemical Industry Co., Ltd.), 25 parts by mass of butyl acetate, 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator 1.2 Hard coat layer paint by mixing and dissolving 11.78 parts by weight of toluene as a solvent, 5.892 parts by weight of 2-propanol, 5.892 parts by weight of ethyl acetate and 5.892 parts by weight of propylene glycol monomethyl ether A composition was obtained.

<Adjustment of antireflection film>
The obtained coating composition for a hard coat layer was applied to a bar coater no. 13 was applied to a PET film having a thickness of 188 μm, and then put into a dryer at 70 ° C. for 1 minute to volatilize the solvent, and an ultraviolet curing device (in a nitrogen atmosphere, using a high-pressure mercury lamp, an ultraviolet irradiation amount of 0.5 kJ) / M ² ) to prepare a hard coat film having a hard coat layer having a thickness of 8 μm on one side. An antireflection coating composition was applied to the bar coater No. 1 on the hard coat layer of the hard coat film obtained above. After coating at 2, the solvent is volatilized by putting it in a dryer at 50 ° C. for 1 minute and 30 seconds, and cured with an ultraviolet curing device (in a nitrogen atmosphere, using a high-pressure mercury lamp, an ultraviolet irradiation amount of ² kJ / m ² ). A film (antireflection film) having an antireflection layer having a thickness of 0.1 μm on the layer was produced. The cured coating film surface of the obtained antireflection film was evaluated for scratch resistance.

<Abrasion resistance evaluation>
Steel wool # 0000 was attached to a 2 cm × 2 cm indenter using a tribogear surface property measuring machine TYPE: 38 manufactured by Shinto Kagaku, and a reciprocation was performed 10 times under a load of 400 g. The number of scratches on the coating surface after the test was counted, and the scratch resistance was evaluated according to the following criteria.
○: The number of scratches is less than 3.
Δ: The number of scratches is 4 or more and less than 10.
X: The number of scratches is 10 or more.

Claims (11)

A low refractive index agent (I);
An active energy ray-curable compound (II);
A fluorine-containing acetophenone derivative (III) which is a Michael adduct of a poly (perfluoroalkylene ether) chain having a (meth) acryloyl group and an α-aminoacetophenone compound capable of generating radical species by photolysis,
An antireflective coating composition comprising: The fluorine-containing acetophenone derivative (III) is
The following general formula (1) or (2)
[In the formulas (1) and (2), A is a direct bond, a divalent or trivalent linking group, m is 1 for a direct bond or a divalent linking group, and a trivalent linking group. m is 2. Y is the following general formula (3) or the following general formula (4)
(X ¹ and X ² are each independently a C 2-6 linear or branched alkylene group or oxyalkylene group which may have a substituent, and X ¹ and X ² are The constituting carbon atoms may be bonded to each other directly or via a linear or branched alkylene group having 2 to 6 carbon atoms which may have a substituent, and X ³ has a substituent. A linear or branched alkylene group or oxyalkylene group having 2 to 6 carbon atoms, and R ⁵ and R ⁶ are each independently an aliphatic group which may have a substituent. An aryl group which may have a group or a substituent),
R is independently a hydrogen atom, a halogen atom or an aliphatic group which may have a substituent, n is each independently an integer of 0 to 4, and R ¹ and R ² are each independently An aliphatic group which may have a substituent or an aryl group which may have a substituent, and R ¹ and R ² may be combined together to form a ring, and R ³ is An aliphatic group which may have a substituent or an aryl group which may have a substituent, R ⁴ is a hydrogen atom, a halogen atom or a monovalent organic group, and PFPE is a poly (perfluoroalkylene) Ether) chain. ]
The antireflective coating composition according to claim 1, which is represented by: R ⁴ in the general formulas (1) and (2) is an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, an aryl group, an aryloxy group, or —X ⁴ —X. ⁵ organic group represented by -X ⁶ [However, X ⁴ is a single bond or a substituent alkylene chain of 1 to 6 carbon atoms which may have a, X ⁵ is carbonyl group, a thiocarbonyl group, —OCONH—, —NHCOO—, or —NHCONH—, and X ⁶ is —NR ⁷ R ⁸ (wherein R ⁷ and R ⁸ are each independently an aliphatic group or a substituent which may have a substituent) An aryl group which may have a group), or the following general formula (5)
(However, X ^7, X ⁸ are each independently a linear or branched alkylene group or an oxyalkylene group having optionally 2 to 6 carbon atoms which may have a substituent, X ⁷ and X ⁸ may be bonded to each other directly or via a linear or branched alkylene group having 2 to 6 carbon atoms which may have a substituent, and X ⁹ is a single atom. A bond, an oxygen atom, or —NR ⁹ — (wherein R ⁹ is a linear or branched alkyl group having 2 to 6 carbon atoms which may have a substituent)]
The antireflective coating composition according to claim 2. Y in the general formulas (1) and (2) represents the following formula (6)
R is hydrogen, R ¹ and R ² are methyl groups, R ³ is an alkyl group having 1 to 4 carbon atoms, and R ⁴ is a hydrogen atom, methyl group, ethyl group, chloro group, bromo group Group or the following formulas (7) to (9)
The antireflection coating composition according to claim 2 or 3, which is any one of the following. Furthermore, the anti-reflective coating composition in any one of Claims 1-4 containing fluorine-type surfactant other than the said fluorine-containing acetophenone derivative (III). The antireflective coating composition according to claim 5, wherein the fluorosurfactant is a compound (IV) having a poly (perfluoroalkylene ether) chain and a polymerizable unsaturated group. Compound (IV) having a poly (perfluoroalkylene ether) chain and a polymerizable unsaturated group is a compound having a structural site having a poly (perfluoroalkylene ether) chain and a polymerizable unsaturated group at both ends thereof ( IV-1) and a copolymer containing the polymerizable unsaturated monomer (IV-2) having a reactive functional group (α) as essential raw materials, and the reactive functional group (α) The antireflection coating composition according to claim 6, which is a reaction product of a reactive functional group (β) having reactivity and a compound (IV-3) having a polymerizable unsaturated group. The antireflective coating composition according to any one of claims 1 to 7, wherein the low refractive index agent (I) is hollow silica fine particles. The antireflection paint according to any one of claims 1 to 8, wherein a blending ratio of the fluorine-containing acetophenone derivative (III) is in a range of 0.01 to 5.0 mass% with respect to a solid content in the composition. Composition. An antireflection film having a cured coating film of the antireflection coating composition according to claim 1. The antireflection film according to claim 10, wherein the cured coating film has a thickness of 50 to 300 nm.